CN114591626B - Transparent polyimide resistant to electron irradiation and stress field coupling and preparation method thereof - Google Patents
Transparent polyimide resistant to electron irradiation and stress field coupling and preparation method thereof Download PDFInfo
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- CN114591626B CN114591626B CN202210258302.3A CN202210258302A CN114591626B CN 114591626 B CN114591626 B CN 114591626B CN 202210258302 A CN202210258302 A CN 202210258302A CN 114591626 B CN114591626 B CN 114591626B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 69
- 239000004642 Polyimide Substances 0.000 title claims abstract description 43
- 230000008878 coupling Effects 0.000 title claims abstract description 10
- 238000010168 coupling process Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- LACZRKUWKHQVKS-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F LACZRKUWKHQVKS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 230000001808 coupling effect Effects 0.000 claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 32
- 229920005575 poly(amic acid) Polymers 0.000 claims description 25
- 238000007605 air drying Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 7
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- -1 N-butylpyridine bis (trifluoromethylsulfonyl) imide salt Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 230000003287 optical effect Effects 0.000 abstract description 19
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- 239000010408 film Substances 0.000 description 23
- 238000002834 transmittance Methods 0.000 description 12
- 239000005457 ice water Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a transparent polyimide material for resisting electron irradiation and coupling stress field and a preparation method thereof, wherein 1, 4-bis (4-amino-2-trifluoromethyl phenoxy) benzene is firstly dissolved in anhydrous N, N-dimethylacetamide, stirred in a water bath at 0 ℃ until the solution is fully dissolved, then hexafluorodianhydride is added to fully react the solution, three different ionic liquids are respectively dripped, fully doped and mixed to obtain transparent polyamide acid, and finally the transparent polyimide material is obtained by placing the transparent polyimide material in a vacuum drying oven for gradient heating and fully thermally imidizing. The transparent polyimide material prepared by the method has excellent optical performance and strong flexibility, wherein the polyimide doped with the 1-ethyl-3-methylimidazole bis (trifluoromethyl) sulfonyl imide ionic liquid has optimal optical and mechanical properties, and has good performance of resisting electron irradiation and stress field coupling effect. The method has the advantages of mild reaction conditions, simple preparation process and low operation cost, and can be used for large-scale production.
Description
Technical Field
The invention relates to a polyimide material and a preparation method thereof, in particular to a transparent polyimide material resistant to electron irradiation and stress field coupling and a preparation method thereof.
Background
Aerospace technology has become an important sign of comprehensive national force at present, and space optics are an integral part of the application of aerospace technology, and have become one of the important means for human exploration of space. The traditional optical imaging system main mirror cannot meet the requirements of deep space exploration on large caliber, light weight, high dimensional stability, foldability and performance stability in space environment, and the thin film main mirror gradually becomes the main stream of space imaging system application. The organic polymer material has the advantages which cannot be compared with other materials, and the application range of the organic polymer material in the field of space optical devices is continuously expanded, wherein polyimide, namely a polymer with a main chain containing imide rings (-CO-N-CO-) with special structures, is widely applied due to the excellent heat stability, chemical stability, dielectric property, mechanical property, radiation resistance and the like.
However, in the field of space application, only the optical performance of the polyimide film is far from being considered, the polyimide film can be subjected to electron, proton, ion, atomic oxygen and other particle irradiation and stress effect generated by cold and hot circulation in the space environment service process, and under the composite effect of the factors, the structural damage of the material can lead to performance reduction and service life shortening, so that potential risk hidden danger is brought.
The colorless transparent polyimide film reported at present cannot give consideration to both optical performance and mechanical performance, and is difficult to resist complex stress fields in space and coupling effect of charged particle irradiation, so that the material performance is greatly reduced, and the requirements of application in the field of space optics cannot be met.
Disclosure of Invention
The invention aims to: the invention aims to provide a transparent polyimide material with high transparency and high flexibility, which resists the coupling effect of electron irradiation and stress field; the invention also aims to provide a preparation method of the transparent polyimide material which has mild reaction conditions and simple operation and can be used for mass production and resists the coupling effect of electron irradiation and stress fields.
The technical scheme is as follows: the invention relates to a transparent polyimide material for resisting electron irradiation and stress field coupling, which has the structural formula:
formula I.
The preparation method of the transparent polyimide for resisting electron irradiation and stress field coupling comprises the following specific steps:
(1) 1, 4-bis (4-amino-2-trifluoromethyl phenoxy) benzene is dissolved in anhydrous DMAc and the solution is between 0 and 5 o Stirring in water bath until the acid is fully dissolved, adding hexafluorodianhydride, continuously stirring in the water bath, and stirring at room temperature to fully react to obtain transparent polyamide acid solution;
(2) Adding fluorine-containing ionic liquid into the transparent polyamic acid solution, and continuously stirring to fully mix the solution;
(3) Uniformly coating the obtained polyamic acid solution on a smooth and clean glass plate;
(4) Drying the glass plate in a vacuum drying oven to ensure that the solvent is fully volatilized, and then carrying out gradient heating to fully thermally imidize the polyamic acid;
(5) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(6) And (5) sucking surface moisture by using filter paper after the film naturally falls off, and naturally air-drying to obtain the transparent polyimide film.
Preferably, the molar ratio of the hexafluorodianhydride to the 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene two monomers is in the range of 1.005 to 1.01.
Preferably, the composite material is introduced into the fluorine-containing ionic liquid only by means of blending doping.
Preferably, the total solids content of the hexafluorodianhydride and 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene monomer is in the range of 10% to 11%.
Preferably, the solid content of the ionic liquid is 5% -6%.
Preferably, the fluorine-containing ionic liquid is 1-ethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide, 1-N-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide or N-butylpyridine bis (trifluoromethylsulfonyl) imide salt.
Preferably, in the step (1), the stirring time in the water bath is 2-3 hours, and the stirring time at room temperature is 10-12 hours; the stirring time in the step (2) is 6-8 h; the drying temperature in the step (4) is 75 to 80 o And C, drying time is 10-12 hours.
The transparent polyimide material can be applied to the coupling effect of electron irradiation resistance and stress field.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The transparent polyimide material with the coupling effect of electron irradiation and stress field prepared by the invention selects 1, 4-bis (4-amino-2-trifluoromethyl phenoxy) benzene containing trifluoromethyl and flexible ether bond as diamine monomer, hexafluorodianhydride as dianhydride monomer, then fluorine-containing ionic liquid is introduced into the system by doping method, and polyimide composite film material with high transparency and high flexibility is synthesized by thermal imidization method, thus improving the defects of poor optical property, low flexibility and the like of the traditional transparent polyimide film; (2) The transparent polyimide material prepared by the invention has excellent optical performance, the optical transmittance at the wavelength of 450nm is more than 85%, and the optical transmittance at the wavelength of 600nm is more than 90.2%; (3) The transparent polyimide material prepared by the invention can still maintain good optical performance under the coupling action of electron irradiation and stress field, and the optical performance is 1 multiplied by 10 16 cm -2 The light transmittance at 600. 600nm was reduced by only 2.7% under electron irradiation of the fluence, and the light transmittance was reduced by 1X 10 at 40% deformation 16 cm -2 The light transmittance at 600nm is reduced by 3.4% under the coupling effect of the fluence electron irradiation; (4) The monomer used in the invention has the advantages of simple and easily obtained raw materials, simple experimental device, low process requirement and convenient operation, and can be used for large-scale production.
Drawings
FIG. 1 is a schematic diagram of a molecular structure of a transparent polyimide;
FIG. 2 is an ultraviolet-visible spectrum of a transparent polyimide;
FIG. 3 is a graph of the UV-visible spectrum of polyimide coupled by stress and electron irradiation.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
The structural formula of the transparent polyimide resistant to the coupling effect of electron irradiation and stress field is shown as the formula I. FIG. 1 is a schematic structural diagram of a transparent polyimide molecule.
Example 1
The preparation method of the transparent polyimide comprises the following steps:
(1) The 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene of 1.0709 g was weighed into a 100 mL round bottom flask, and 20 mL of N, N-dimethylacetamide was added to the flask and stirred in an ice water bath until fully dissolved;
(2) Weighing 1.1217 g, adding hexafluorodianhydride into the mixed solution of the above (1), and adding 0 o Stirring for 3 hours under the water bath, and stirring for 12 hours at room temperature to fully react;
(3) Slowly dropwise adding 1.1013 g 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimide into the solution (2), and continuously reacting for 8 hours to obtain a corresponding polyamic acid solution.
(4) Uniformly coating the polyamic acid solution on a smooth and clean glass plate, and placing the glass plate into a vacuum drying oven;
(5) Regulating the temperature of the drying box to 80 DEG C o C, keeping for 12 hours, ensuring that the solvent is fully volatilized, then carrying out gradient heating, and sequentially adjusting the temperature of a drying box to be 110 o C/2h、150 o C/2h、170 o C/2h、190 o C/2h；
(6) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(7) And after the film naturally falls off, sucking the surface moisture by using filter paper and naturally air-drying to obtain the transparent polyimide film S1.
Example 2
The preparation method of the transparent polyimide comprises the following steps:
(1) The 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene of 1.0709 g was weighed into a 100 mL round bottom flask, and 20 mL of N, N-dimethylacetamide was added to the flask and stirred in an ice water bath until fully dissolved;
(2) Weighing 1.1217 g, adding hexafluorodianhydride into the mixed solution of the above (1), and adding 0 o Stirring for 3 hours under the water bath, and stirring for 12 hours at room temperature to fully react;
(3) Slowly dropwise adding 1.1013 g 1-n-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide into the solution (2), and reacting for 8 hours to obtain a corresponding polyamic acid solution.
(4) Uniformly coating the polyamic acid solution on a smooth and clean glass plate, and placing the glass plate into a vacuum drying oven;
(5) Regulating the temperature of the drying box to 80 DEG C o C, keeping for 12 hours, ensuring that the solvent is fully volatilized, then carrying out gradient heating, and sequentially adjusting the temperature of a drying box to be 110 o C/2h、150 o C/2h、170 o C/2h、190 o C/2h；
(6) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(7) And after the film naturally falls off, sucking the surface moisture by using filter paper and naturally air-drying to obtain the transparent polyimide film S2.
Example 3
The preparation method of the transparent polyimide comprises the following steps:
(1) The 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene of 1.0709 g was weighed into a 100 mL round bottom flask, and 20 mL of N, N-dimethylacetamide was added to the flask and stirred in an ice water bath until fully dissolved;
(2) Weighing 1.1217 g, adding hexafluorodianhydride into the mixed solution of the above (1), and adding 0 o Stirring for 3 hours under the water bath, and stirring for 12 hours at room temperature to fully react;
(3) Slowly dropwise adding 1.1013 g N-butylpyridine bis (trifluoromethanesulfonyl) imide salt into the solution (2), and reacting for 8 hours to obtain a corresponding polyamic acid solution.
(4) Uniformly coating the polyamic acid solution on a smooth and clean glass plate, and placing the glass plate into a vacuum drying oven;
(5) Regulating the temperature of the drying box to 80 DEG C o C, keeping for 12 hours, ensuring that the solvent is fully volatilized, then carrying out gradient heating, and sequentially adjusting the temperature of a drying box to be 110 o C/2h、150 o C/2h、170 o C/2h、190 o C/2h；
(6) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(7) And after the film naturally falls off, sucking the surface moisture by using filter paper and naturally air-drying to obtain the transparent polyimide film S3.
Example 4
The preparation method of the transparent polyimide comprises the following steps:
(1) The 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene of 1.0709 g was weighed into a 100 mL round bottom flask, and 20 mL of N, N-dimethylacetamide was added to the flask and stirred in an ice water bath until fully dissolved;
(2) Weighing 1.1217 g, adding hexafluorodianhydride into the mixed solution of the above (1), and adding 0 o Stirring for 3 hours under the water bath, and stirring for 12 hours at room temperature to fully react;
(3) Slowly dropwise adding 1.1013 g 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimide into the solution (2), and continuously reacting for 8 hours to obtain a corresponding polyamic acid solution.
(4) Uniformly coating the polyamic acid solution on a smooth and clean glass plate, and placing the glass plate into a vacuum drying oven;
(5) Regulating the temperature of the drying box to 80 DEG C o C, keeping for 12 hours, ensuring that the solvent is fully volatilized, then carrying out gradient heating, and sequentially adjusting the temperature of a drying box to be 110 o C/2h、150 o C/2h、170 o C/2h、190 o C/2h；
(6) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(7) And (5) sucking surface moisture by using filter paper after the film naturally falls off, and naturally air-drying to obtain the transparent polyimide film.
(8) The obtained film was subjected to a 1 MeV betting amount of 2X 10 by using DD1.2 electron accelerator 14 e/cm 2 Is marked S4.
Example 5
The preparation method of the transparent polyimide comprises the following steps:
(1) The 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene of 1.0709 g was weighed into a 100 mL round bottom flask, and 20 mL of N, N-dimethylacetamide was added to the flask and stirred in an ice water bath until fully dissolved;
(2) Weighing 1.1217 g, adding hexafluorodianhydride into the mixed solution of the above (1), and adding 0 o Stirring for 3 hours under the water bath, and stirring for 12 hours at room temperature to fully react;
(3) Slowly dropwise adding 1.1013 g 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimide into the solution (2), and continuously reacting for 8 hours to obtain a corresponding polyamic acid solution.
(4) Uniformly coating the polyamic acid solution on a smooth and clean glass plate, and placing the glass plate into a vacuum drying oven;
(5) Regulating the temperature of the drying box to 80 DEG C o C, keeping for 12 hours, ensuring that the solvent is fully volatilized, then carrying out gradient heating, and sequentially adjusting the temperature of a drying box to be 110 o C/2h、150 o C/2h、170 o C/2h、190 o C/2h；
(6) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(7) And (5) sucking surface moisture by using filter paper after the film naturally falls off, and naturally air-drying to obtain the transparent polyimide film.
(8) Applying a strain quantity with a stretching ratio of 40% to a film sample by using a high-precision pulling machine, clamping for a period of time, and obtaining a transparent polyimide film with a longitudinal stretching deformation of 40% after a long-time relaxation process;
(9) The obtained film was subjected to a 1 MeV betting amount of 2X 10 by using DD1.2 electron accelerator 14 e/cm 2 Is marked S5.
Example 6
The preparation method of the transparent polyimide comprises the following steps:
(1) The 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene of 1.0709 g was weighed into a 100 mL round bottom flask, and 20 mL of N, N-dimethylacetamide was added to the flask and stirred in an ice water bath until fully dissolved;
(2) Weighing 1.1217 g, adding hexafluorodianhydride into the mixed solution of the above (1), and adding 0 o Stirring for 3 hours under the water bath, and stirring for 12 hours at room temperature to fully react;
(3) Slowly dropwise adding 1.1013 g 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimide into the solution (2), and continuously reacting for 8 hours to obtain a corresponding polyamic acid solution.
(4) Uniformly coating the polyamic acid solution on a smooth and clean glass plate, and placing the glass plate into a vacuum drying oven;
(5) Regulating the temperature of the drying box to 80 DEG C o C, keeping for 12 hours, ensuring that the solvent is fully volatilized, then carrying out gradient heating, and sequentially adjusting the temperature of a drying box to be 110 o C/2h、150 o C/2h、170 o C/2h、190 o C/2h；
(6) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(7) And (5) sucking surface moisture by using filter paper after the film naturally falls off, and naturally air-drying to obtain the transparent polyimide film.
(8) The obtained film was subjected to a 1 MeV betting amount of 2X 10 by using DD1.2 electron accelerator 15 e/cm 2 Is marked S6.
Example 7
The preparation method of the transparent polyimide comprises the following steps:
(1) The 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene of 1.0709 g was weighed into a 100 mL round bottom flask, and 20 mL of N, N-dimethylacetamide was added to the flask and stirred in an ice water bath until fully dissolved;
(2) Weighing 1.1217 g, adding hexafluorodianhydride into the mixed solution of the above (1), and adding 0 o Stirring for 3 hours under the water bath, and stirring for 12 hours at room temperature to fully react;
(3) Slowly dropwise adding 1.1013 g 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimide into the solution (2), and continuously reacting for 8 hours to obtain a corresponding polyamic acid solution.
(4) Uniformly coating the polyamic acid solution on a smooth and clean glass plate, and placing the glass plate into a vacuum drying oven;
(5) Regulating the temperature of the drying box to 80 DEG C o C, keeping for 12 hours, ensuring that the solvent is fully volatilized, then carrying out gradient heating, and sequentially adjusting the temperature of a drying box to be 110 o C/2h、150 o C/2h、170 o C/2h、190 o C/2h；
(6) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(7) And (5) sucking surface moisture by using filter paper after the film naturally falls off, and naturally air-drying to obtain the transparent polyimide film.
(8) Applying a strain quantity with a stretching ratio of 40% to a film sample by using a high-precision pulling machine, clamping for a period of time, and obtaining a transparent polyimide film with a longitudinal stretching deformation of 40% after a long-time relaxation process;
(9) The obtained film was subjected to a 1 MeV betting amount of 2X 10 by using DD1.2 electron accelerator 15 e/cm 2 Is marked S7.
Example 8
The preparation method of the transparent polyimide comprises the following steps:
(1) The 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene of 1.0709 g was weighed into a 100 mL round bottom flask, and 20 mL of N, N-dimethylacetamide was added to the flask and stirred in an ice water bath until fully dissolved;
(2) Weighing 1.1217 g, adding hexafluorodianhydride into the mixed solution of the above (1), and adding 0 o Stirring for 3 hours under the water bath, and stirring for 12 hours at room temperature to fully react;
(3) Slowly dropwise adding 1.1013 g 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimide into the solution (2), and continuously reacting for 8 hours to obtain a corresponding polyamic acid solution.
(4) Uniformly coating the polyamic acid solution on a smooth and clean glass plate, and placing the glass plate into a vacuum drying oven;
(5) Regulating the temperature of the drying box to 80 DEG C o C, keeping for 12 hours, ensuring that the solvent is fully volatilized, then carrying out gradient heating, and sequentially adjusting the temperature of a drying box to be 110 o C/2h、150 o C/2h、170 o C/2h、190 o C/2h；
(6) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(7) And (5) sucking surface moisture by using filter paper after the film naturally falls off, and naturally air-drying to obtain the transparent polyimide film.
(8) The 1 MeV betting amount of the obtained film was 1X 10 by using DD1.2 type electron accelerator 16 e/cm 2 Is marked S8.
Example 9
The preparation method of the transparent polyimide comprises the following steps:
(1) The 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene of 1.0709 g was weighed into a 100 mL round bottom flask, and 20 mL of N, N-dimethylacetamide was added to the flask and stirred in an ice water bath until fully dissolved;
(2) Weighing 1.1217 g, adding hexafluorodianhydride into the mixed solution of the above (1), and adding 0 o Stirring for 3 hours under the water bath, and stirring for 12 hours at room temperature to fully react;
(3) Slowly dropwise adding 1.1013 g 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimide into the solution (2), and continuously reacting for 8 hours to obtain a corresponding polyamic acid solution.
(4) Uniformly coating the polyamic acid solution on a smooth and clean glass plate, and placing the glass plate into a vacuum drying oven;
(5) Regulating the temperature of the drying box to 80 DEG C o C, keeping for 12 hours, ensuring that the solvent is fully volatilized, then carrying out gradient heating, and sequentially adjusting the temperature of a drying box to be 110 o C/2h、150 o C/2h、170 o C/2h、190 o C/2h；
(6) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(7) And (5) sucking surface moisture by using filter paper after the film naturally falls off, and naturally air-drying to obtain the transparent polyimide film.
(8) Applying a strain quantity with a stretching ratio of 40% to a film sample by using a high-precision pulling machine, clamping for a period of time, and obtaining a transparent polyimide film with a longitudinal stretching deformation of 40% after a long-time relaxation process;
(9) The 1 MeV betting amount of the obtained film was 1X 10 by using DD1.2 type electron accelerator 16 e/cm 2 Is marked S9.
As shown in FIG. 2, the polyimide films obtained by doping three different fluorine-containing ionic liquids have different optical properties, but the optical transmittance of the three films at the wavelength of 450nm is more than 85%, the optical transmittance at the wavelength of 600nm is more than 90.2%, wherein the S1 optical property doped with 1-ethyl-3-methylimidazole bistrifluoromethylsulfonylimine is the most excellent, and the optical transmittance at the wavelength of 600nm is as high as 90.85%.
As shown in FIG. 3, the transparent polyimide film S1 which is not subjected to longitudinal stretching and electron irradiation has good optical properties, and has a cut-off wavelength of 319 nm and a transmittance at 600nm of as high as 90.85%. As the fluence of irradiation increases, the optical transmittance of the transparent polyimide film also gradually decreases. At 2X 10 14 cm -2 、2×10 15 cm -2 、1×10 16 cm -2 Three kinds of non-woven fabricsThe light transmittance of the transparent polyimide films S4, S6 and S8 under the same electron irradiation fluence at 600nm is 90.58 percent, 89.67 percent and 88.34 percent respectively, and the reduction rate of the transparent polyimide films is 0.24 percent, 1.24 percent and 2.7 percent respectively compared with the original films; the transmittance of the transparent polyimide films S5, S7 and S9 under the coupling effect of 40% deformation and three electron irradiation fluence at 600nm is 90.03%, 89.44% and 87.71%, respectively, and the reduction rates of the transparent polyimide films are 0.85%, 1.5% and 3.4% respectively compared with the original films. The polyimide film can still keep excellent optical performance under the effects of electron irradiation and stress coupling, and provides a basis for the application prospect of the material in the field of space optics.
Claims (8)
1. The application of the transparent polyimide material in the coupling effect of electron irradiation resistance and stress field is characterized in that the structural formula of the transparent polyimide material is as follows:
the material is prepared by the following steps:
(1) Dissolving 1, 4-bis (4-amino-2-trifluoromethyl phenoxy) benzene in anhydrous DMAc, stirring in a water bath at 0-5 ℃ until the benzene is fully dissolved, adding hexafluorodianhydride, continuously stirring in the water bath, and stirring at room temperature to fully react to obtain a transparent polyamic acid solution;
(2) Adding fluorine-containing ionic liquid into the transparent polyamic acid solution, and continuously stirring to fully mix the solution;
(3) Uniformly coating the obtained polyamic acid solution on a smooth and clean glass plate;
(4) Drying the glass plate in a vacuum drying oven to ensure that the solvent is fully volatilized, and then carrying out gradient heating to fully thermally imidize the polyamic acid;
(5) Naturally cooling the drying box to room temperature, taking out the glass plate and soaking the glass plate in normal-temperature deionized water;
(6) And (5) sucking surface moisture by using filter paper after the film naturally falls off, and naturally air-drying to obtain the transparent polyimide film.
2. The use of a transparent polyimide material according to claim 1, wherein the molar ratio of the hexafluorodianhydride to the 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene monomers is in the range of 1.005-1.01.
3. Use of a transparent polyimide material according to claim 1 for the coupling of electron irradiation and stress fields, wherein the transparent polyimide material is incorporated into a fluorine-containing ionic liquid by means of only co-doping.
4. Use of a transparent polyimide material according to claim 1, wherein the total solids content of the hexafluorodianhydride and 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene monomers is in the range of 10% to 11%.
5. The use of a transparent polyimide material according to claim 1, wherein the fluorine-containing ionic liquid has a solids content of 5% to 6% in the coupling of electron irradiation and stress field.
6. Use of a transparent polyimide material according to claim 1, wherein the fluorine-containing ionic liquid is 1-ethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide, 1-N-butyl-1-methylpyrrolidine bis (trifluoromethylsulfonyl) imide or N-butylpyridine bis (trifluoromethylsulfonyl) imide salt.
7. The use of a transparent polyimide material according to claim 1 for the coupling of electron irradiation resistance and stress field, wherein the stirring time in the water bath of step (1) is 2 to 3 hours and the stirring time at room temperature is 10 to 12 hours; and (3) stirring for 6-8 h in the step (2).
8. The use of a transparent polyimide material according to claim 1, wherein the drying temperature in step (4) is 75-80 ℃ and the drying time is 10-12 hours.
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